matich no.t pp. 125-134 4975 THE VALUE OF TOPOLOGICAL INDICES IN CHEMISTRY D. H. Rouvray+ -Chemistry Department, University of the Witwatersrand, Johannesburg, South Africa In recent years it has become increasingly apparent that many, if not all, physical and chemical properties of fluids are dependent upon and often largely determined by the topological structure of their component chemical ew of this development, it would thus not be unreaccnable to describe chemictry today ac an cocent- species. In v ially topological subject!. In this paper, ve briefly review sexe of the principal areas of activity which have led to this new situation. We start by tracing these areas back to their origins The earliest work along these lines, was that involving studies of the additive properties cf compounds, initiated during the first haif of the nineteenth century. As an exemple, we cite the work cf Xopp?, who demonstrated that the thermodynamic parameters of compounds such as boiling point and specific heat were roughly additive in the eense that an approxizately constant difference in the parameter was observed for compounds differing by @ given chemical grouping, such as a methylene unit. He was also the et person tc express his results in the form of algebraic equations. During the succeeding decades, Kepr's researches were extended by a variety cf vorkers, One of these, Markownikey, showed that the elting point of a branched hydrocarbon is higher then that for the corresponding straight chein species?.- 126 ~ In the present century, Fiickel developed his now famous procedures for obtaining appproximate answers to the Schrédinger equation for hydrocarbon species". Extensions to his work, by investigetors such as Coulson’, led to the introduction of several new quantum chemical parameters characteristic of hydrocarbon species, These included the t-electronic charge density, the bond order, and the polarizabilit; y. In the early 1950's it was demonstrated by Ruedenberg® that all such parameters were dependent upon the molecular topology. Shortly thereafter, the correspondence between the Hlckel matrix end what is now referred to as the topological matrix was pointed out by Alkanes to C,,- Viscosity at 308,15K Standard Deviation = 0,052 log, (viscosity) -05 fo& log! a w a oO ‘ogg! ~ - 127 - Alkanes to C,,- Surface Tension at 29315K Standard Deviation = 0,021 logg(surface tension) 28 29 30 31 32 Alkanes to C,- Refractive Index Standard Deviation = 0,002 logglrefractive index) 29 30 31 32 33 3h- 128 - Atkanes to C)- Boiling Point 6 5 2 8 42 3 2 Standard Deviation = 0,005 1 loge (boiling point) l §2 54 56 53 60 62 Alkanes to C,.- Melting Point 6 a 4 3 2 Standard Deviation = 0,087 tog, (melting point) 48 49 §0 51 52-53 54 55 56- 129 - Alkanes to Cj~ Density 6 log, 5 h 3 Standard deviation = 0,013 log, (density) 04% "05 06 Alkenes to C,,- Surface Tension at 293,15 K 7 6 5 ae 4 3 Standard Deviation = 0,050 log! log, (surface tension) 25 26 27 28 29 30 “31 32 33- 130 - Alkynes to C,,-Melting Point loge! a, a Standard Deviation = 0.064 loge (melting point) 56° 55 56 5) 52 53 57 loge! o Standard Deviation = 0,008 loge (boiling point) 58 59 60 6 62 63 64.65 66 67= 131 - Glnthard and Prinas?. The Pairing Theorem is also realised to be @ greph-theoretical result in essence®, Many original contributions to this general area have been made within the last five years by Gutman and Trinajstié?. The evolution of topological indices in their own right has come about during the last decade. The results obtained in this area up to 1973 have been reviewed by the present author!®, The fundamental idea in this approach is that @ topological index of the structure of a component species should reflect the bulk properties of the fluid formed from the species in question. The condition that all such species belong to a given chemical series, ensures that interactions between species will ell be of the same general type. By making this condition, intermolecular forces may thereafter be neglected, at least to a first approximation. To date fairly good correlations have been obtained with topological indices and the boiling points of members of several homologous serics. Examples of euch correlations are to be found in the works of Kosoya!! and Ranaiél?. Por members of these series beyond about Cys, however, the correlations have frequently been rather poor. In an attempt to overcome these setbacks, the present author developed a nev index, designed to be valid for a uch wider range. ‘The new index proposed is based on the distance matrix of a chemical species. The index is derived by simply summing ell the entries in this matrix, and so the new index is given by the summation Although in such an index the structure within the matrix is lost, it vas thought that this index might provide e better representation of a species than some of the other indices previously proposed, because it differentiates more clearly betveen cinilar structures such as 2-nethyl hexane and 3-nethyl hexane. In practice, we have found good to excellent correl-- 132 - ations between our index and the bulk parameters of iiquids. In our vork we considered the members of the alkene, alkene, and alkyne homologous series up to the Cyg members, and arenes up to the Cag members. Using these molecules, ve looked for correlations of our index against boiling point, melting point, surface tension, viscosity, density, and refractive index. A relationship of the general form P= ky (x)#2 was assumed, where P is the bulk physicochemical parameter, ky and kp are constants to be determined for a given series, and I is our index, In all cases In P was plotted against An I to test the reletionship. Our investigations have revealed that in all cases « correlation cf the type assumed does exist. Por the first dozen or so merbers of all series investigated a fairly good approximation to a straight line was obtained, The best correlations were obtained for boiling points, and the worst for melting points. Standard deviations vere usually of the order cf 0,01 or less in this range. After the first dozen or so members, the plots assumed a distinct curvature, and standard deviations became correspondingly poorer. All plots were found to be convex with respect to the In I axis, vith the exception of the viscosity plots which were always concave. The shapes of the curves may be accounted for on the following qualitative basis. We suppose that the molecular topology is of overriding influence in determining physico- chemical parameters vithin @ given series, as the inter- molecular forces may ail be assumed of the same type. This supposition explains in general terms the correlations ve have found. But, because molecules are not rigid, we can expect an increasing amount of folding and bending in the liquid phase as the carbon content increases. As a result of this, a relatively large molecule folded into the form of a hairpin might behave as a molecule of only one half its true length. Such folding would emount to an effective loss of topological structure, which should become more Pronounced vith increasing carbon content. This would lead- 133 - to @ progressive lowering of the effective value of our index, and-thus to the convex curves which we obtained. In the case of the viscosity plots, a loss of topological structure should result in @ reduced resistance to flow, and therefore to an increased viscosity. On this basis a concave curve is thus to be expected. Work is now undervay to make these qualitative explanations quantitative by study of simulated liquid structures, The relatively poor correl- ations with melting points may be due to the fect that lattice forces are superimposed upon the usual intermolecular forces, and these to some extent modify the force field in which the molecules find themselves. Lattice forces being relatively independent of topological structure, it is only to be expected thet poor correlations were found for this parameter. In conclusion, we may say that, because our correlations were generally good, that the importance of topology as a determinant of physicochemical behaviour has been established. In fact, in some cases the correlations vere so good that it would be feasible to make predictions of unknown parameters from our index. Furthermore, the curvature found for all our plots might be utilized to provide information on the intermolecular forces in liquids and the relative arrangement of the molecules in this phase. Up to the present, the only type of parameters to have been investigated have been those of a physical or chemical nature. In future, it may prove possible to correlate biological parameters against e suitable index. Work is at present underway in Johannesburg to correlate the degree of carcinogenicity in arene species in this way. It vould thus eppear that this fruitful new line of inquiry is far from exhausted.- 134 - References lo. ll. R.W. Jotham, Chem. Soc. Reviews 2, 457 (1973). H. Kopp, Ann, Chem. bi, 79, 169 (182). V.V. Markovnikey, Ann. Chem. 162, 324 (1876). EB. Hickel, Z. Phys. 70, 204, 279 (1931); idem. ibia. 12, 310 (1931). C.A. Coulson, Proc. Roy. Soc. London A169, 413 (1939). K. Ruedenberg, J. Chem. Phys. 22, 1878 (1954). H.H. Gunthard and H. Primas, Helv. Chim. Acta 39, 1645 (1956). D. Cvetkovié, Publ. Fac. Electrotechnique, Ser. Mat. Fiz. (univ. Belgrade) 354-356, 1 (1971). I. Gutman and N. Trinajstié, Topics in Curr. Chem. 42, 49 (1973). D.H. Rouvray, Amer. Sci. 61, 729 (1973). H. Hosoya, Bull. Chem. Soc. Japan Uh, 2332 (1971). . Randié, J. Amer. Chem. Soc., to appear.